Method of cracking oils



March 2.6, 1929. v J. R. MARDICK 1,705,629

' METHOD 'oF cRAoxmG oxL's.

Filed. "May 5, 1925.

` INVENToRs 1kb/ATTORNEY JOHN R.

Mannion, or NewA YORK, N. Y.,

1,766,629 PATENT OFFICE.

ASSIGNOR TO UNIERSAL OIL PRODUCTS (JOIVIIPANY,n OF CHICAGO, ILLINOIS, A CORPORATION OF SOUTH DAKOTA.

METHOD OF CRACKING OILS.

applieation filed may 5, 1923. serial No. 637,012.

rl`his invention relates to the treatment of petroleum oils in'order to improve the yield and quality of the distillates obtainable therefrom, and particularly from petroleum residues, and has for its principal objects the expeditious and economical production of high test distillates, such for example as gasolene, kerosene, lubricating oils and the like from petroleum residues resulting from the removalv ofthe natural gasolene and kerosene from cru-de petroleum oil as well as further objects as will more in detail and at length appear in the following description.l

lt is well known that elements in their nascent or freshly liberated condition are far more active than the same elelnents in ordinary or non-nascent condition. The crux of my invention'colnsists in the utilization of chlorine which has been previously rendered l active so as to substantially correspond to chlorine in a nascent condition, while at the same time avoiding the presence, of objectionable elements, -such a's compounds of aluminum for example, which result from the well-known catalytic conversion of high boiling petroleum oils into lower boiling point petroleum oils by the employment of erties to the light distillates resulting from aluminum chloride.

My investigations have lead to thediscovery that ordinary chlorine, for example such as obtained by the electrolysis of brine is, when properly activated in the manner hereinafter described, peculiarly suited for einployment in the production of sweet, resin.- and gum-free gasolene, kerosene, lubricating oil and like relatively 10W boiling point distillates from high boiling point petroleum residue. A

ln the accompanying drawing, I have illustrated an apparatus well known in the art suitable for activating the chlorine, al-

though other suitable apparatus may be emp ployed in' lieu thereof, the view shown being a vertical section.

Referring to the drawings and the construction shown therein, the reference numerall designates the metallic casin of a' reaction chamber a, in which cham er is mounted a discharge electrode ,2, which is from an insulated support 3 that suspended connected to a high potential ciris in t-urn cuit, such production of an electric corona- At the 4 bottom of said casing I provide an inlet. et

for the admission of dehydrated, and preftheir as is commonly employed for the erably preheated, chlorine and at the top of said casing is an outlet 5 which is adapted to conduct the activated chlorine obtained in said apparatus to a still or absorption tower wherein the activated chlorine is brought into intimate contact with dehydrated oils or oil residues, also preferably preheated as hereinafterv described, which Ait is desired to subject to the action of such activated chlorine. i

In carrying out my invention ably proceed as follows:

^ A'petroleum residue such as gas-oil having a boiling point of, say, 250 C. and upwardly, which is obtained by the preliminary heating or topping of cru-de petroleum to remove moisture and the lighter distillates therefrom that are natural to the petroleum is heated to a temperature of, say, 300 C. and while so heated is intimately mixed Yin any desired manner with activated chlorine prevpared preferably in the manner herein described.A The supply of chlorine, if too rapid, would result in the formation of gummy, resinous solids which will not only interfere with the operation and the yield obtainable thereby, but will impart objectionable propl prefer- 1 lubricating oils whichv are obtained from the high boiling point residue will be substantially free from gums and resin, but not so low that the quantity of light distillates boiling below 230 C. will be insuiiicient for the satisfactory commercial operation of the rocess. A suitable proportion of chlorine activated in the manner hereinafter described, for admixture with gas-oil obtained from such oils for example as Pennsylvania and crude oils (paratlin type) or Oklahoma crude oils (paraffin and asphaltic types) is from one-half to onev percent of chlorine upon the weight of the oil residues treated, the rate of supply being, however, in all cases primarily determined by the aforesaid characteristics and yield of the lower boiling point distillates. Preferably the chlorine is supplied at about five pounds pressure per square inch.

-vgether in a tower, filled with inert material,

in which the oil residue Hows downwardly from the top and the chlorine iows upwardly in the opposite direction being brought atl intimate contact with each other by passage over the inert material, which latter may also be suitably heated if desired. In certain cases it may be'also` desirable to effect the mixture of the activated chlorine with oil vaporsresulting from the heating of such oil c residue, such mixture preferably'being also effected in a tower filled with heated inert material. y A l I My activated chlorine .which is suitable for utilization in the aforesaid process is prepared by dehydrating ordinary chlorine which is either obtained by the electrolysis of brine or purchased in a compressed condition, such dehydration. being edected by causing the sameto pass through concentrated sulphuric, acid of 60 to 660 B. strength preferably and also through solid calcium chloride, or in' any other satisfactory manner. The object of such dehydration of both the chlorine as well as the oilv residue is to prevent the destruction of the activated chlorine by interaction of such water with consequent great reduction in yield of lower boiling point distillates obtained by the op eration of the. process.

The activation of such previously dried chlorine is effected by causing the passage thereof through an electrical apparatus such as yan electrical ozonizer or preferably through an electrical apparatus inlwhich the chlorine'is subjeted to the activating iniuence of attenuated arcs or sparks of the violet ray type such as is commonly employed inl electrical precipitation by the well lknown Cotrell process or by the well known corona discharge apparatus, such as disclosed in the patent to W. A. Schmidt and E. R. Wollcott No. 1,307,930 of June 24, 1919 and the patent to W. A. Schmidt and G. C. Roberts No. 1,343,482 of June 15, 1920.y v

Chlorine activated as aforesaid is then admiXed with the oil residues, or the vapors thereof in the manner hereinbefore described and preferably such chlorine ispreheated immediately before being admixed with such oil residues or the vapors thereof, although when so' preheated care must be taken that the temperature does'not exceed that at which the activity of the chlorine will be destroyed. 'While I preferably employ about five pounds ofpressure in operating my preferred process,.l I may, if desired, operate the same vunderseveral atmospheresof pressure, say,

` impurities and Vits other desirable properties,

-be useful and essential.

corrosion thereof, in view ofthe fact that the oil residue and the chlorine are in a dehydrated condition, and furthermore the resultant coke obtainable by the operation of this process is, unlike that obtainable by catalytic conversion processes employing aluminum chloride, free from inorganic impurities -such as aluminum oxide, and therefore is peculiarly valuable for metallurgical and electrochemical purposes wherein -such a carbon product would, because of-its freedom from Not'only is my process peculiarly adapted for the treatmentyof oil residues of the paraffin type, but even oil residues of the asphaltic type and particularly of the asphaltic and paraffin type, as well as oil residues containing substantial quantities of sulphur, can be materially improved by treatment in accordance with my process.

The gasolene, kerosene and lubricating oils -obtained from theitreatment of suitable petroleum residues by my improved process and particularly those obtainable from the treatment of Pennsylvania and Louisiana petroleum residues are relatively free from unsaturated hydrocarbons and will not form any appreciable amount of tarry substances when treated with funiing'sulphuric acid in the manner customary in treating such products in order toV 'remove unsaturated hydro- 105 carbon therefrom. In fact, gasolene obtainable by my improved process can berretined without theemployment of sulphuric acid as it merely yrequires washing with alkali in order to make a highly satisfactory product. Furthermore, such gasolene, kerosene' and lubricating oils obtained through the employment of my process are, as heretofore stated, peculiarly free from resins and gums and furthermore owing to the absence of objectionable, odoriferous,unsaturated hydrocarbons in any large quantity are peculiarly sweet and water-white or transparent. y

The unusually effective cracking vaccomplished by the hereindescribed treatment of oils can best be explained as an electron phenomenon. For example, it is well known that atoms consist of even smaller particles which are termed electrons and the latter when the atoms have been freshly liberated from their polarity and thereby the atomic and molecular activity of any particular element' under observation becomes materially impaired or lessened.

In the case of chlorine, it has been established that. two different kinds of atoms exist ,each having characteristic groupingsof electrons and atomic weights. When electrically activated through the influence of a high potential electric current, however, it is believed that there is a substantial energizing of the atoms by causing a movement of the electrons from the inner to outer orbits with the Apossible consequence of a radical regrouping of the electrons or even the atoms themselves in a manner somewhat akin to the 'change produced by an ozonizing electrical current upon oxygen. The foregoing explanation accounts for the fact that the inactive chlorine atoms either become highly active or have their original activity restored upon being activated in the manner herein described.

My improved process may either be conducted as a continuous or an intermittent .process and may be applied to other oil "residucs than those boiling upwardly from 250o C., it being especially serviceable for cracking keroseneinto gasolene hydrocarbons in those cases when the latter can be disposed of to better advantagethan the kero! sene.

Preferably. I employ reflux condenser of the type commonly employed in this art and return to the still the vapors condensing below certain desired temperatures for further treatment. Ordinarily a period of treatment of from 24 to 36 hours will suiice to effect the conversion within economic limits of cost of substantially all of the convertible 'i portions of the oil treated to the lower boiling point distillates. i

In' those caseswhere it is merelyA desired to effect the improvement of the oil treated, as lnow as lgth of a percent of activated chlo rine, based on the weight ofthe oil, will be found to be useful, but for the production of low boiling point hydrocarbons, particularly those of the gasolene type, I nd it advisable to employ at least llth of.1% of activated chlorine and preferably between 1/,3' of 1% and 1% as previously stated. In practically no instance, regardless of the oil treated, should the amount of activated chlorine exc'eed 2% of the weight of the oil treated. Furthermore, the temperature of treatment will like- Wise depend upon the character of the distillates desired. For example, for improving lubricating oils without effecting undue cracking thereof, a low temperature of treatment is desirable, i. e. approximately between 60Cl C. and 7 50 C., whereas, if a high yield of low boiling point hydrocarbons such, for example, as hydrocarbons within the range of gasolene (i. e.v those having a boiling point up to approximately 230 C.. is deslred, it is important that the temperature employed should more closely approximate the boiling point of the residue under the pressure at lwhich it is subjected in the treatment.

Depending upon the character of the resilglues employed, it is possible to obtain an amount of low boiling point hydrocarbons of the gasolene range in amounts ranging from 415%, and in some instances up to even 45% of the weight of the oil residue treated.

' As is evident from .the foregoing descrip-4 tion, my improved process possesses the peculiar advantage over the well known catalyticl conversion processes employing aluminum chloride of avoiding the necessity 0f removing aluminum chloride from the coke-containing sludge remaining in the still after the removal of the gasolene, kerosene and like burning oil distillates, in order to f produce high quality lubricating oils therefrom.' Notwithstanding moreover, the fact that in suchv aluminum chloride process, the aluminum chloride may be recovered to a substantial extent, nevertheless, it will be found that the employment of activated chlorine, in the manner herein described, is far more economical and produces higher grade products than it is possible to obtain by such prior 'methods utilizing'aluminum chloride.

While I have disclosed the employment of electrically activated chlorine because ofits cheapness', lthe substitution therefor of the well known chemical equivalents is equally withinthe scope of the appended claims.

Having thus described. my invention, what I claim is:

. 1..'I`he method of cracking oil which comprises'heatinga high boiling point oil, and subjecting such oil to the action of previo usl v electrically activated chlorine in the absence of sufficient moisture to materially interfere with such cracking operation, and then collecting the relatively low boiling point distillates obtained by such treatment.

2.- The method of -cracking high .boiling point petroleum oil in order to obtain therefrom gasoline hydrocarbons, including those of the gasoline range, which comprises sub- ]ecting petroleum oil having a boiling point in excess of 230o C. to the action of free chlorine gas introduced from an external source into such oil While in the absence of sufficient moisture to seriously interfere with the cracking operation, the chlorine when se introduced being ina highly active state due to the energizing of the atoms thereof while in substantially anhydrous condition and then recovering the low boiling point hydrocarbons resulting from such treatment.

3. In the process -of cracking petroleum oil, the stepwhich consists in subjecting a petroleum residue having a boiling point in excess of 230 C. to the action of previously activated chlorine gas while in the absence of suiicient moisture to seriously interfere with the cracking operation, saidchlorine gas being introduced into said oil residu-e in a gaseouscondition. 4.i In the process of cracking petroleum, the steps Whichgconsist in subjecting dehydrated residual petroleum oils to the action of l.activated chlorine substantially free from iny organic chlorine-compounds foreign to such oil in its untreated condition, the time of treatment, the temperature of treatment andthe cient toeffect the conversion of such residue into low boiling point hydrocarbons to the extent of at least 425% of the Weight of the vresidue treated. v

- 5I In the process ofcracking petroleum oil,

^ the step Which consists in subjecting a high boiling point petroleum oil residueto the action 'of previously activated chlorine gas While in the absence of suicient moisture tol seriously interfere With the cracking operaainount of such chlorine employed being suii@ nal source under a super atmospheric pressurel into such oil, the chlorine so introduced being in a highly active state due to the activation thereof While free from sufficient Water to preventeffective activation thereof by a high potential electric current andthen recovering the low boiling point hydrocarbons resulting from such treatment.

8. In the process of improving residuum petroleum oil-the step which consists in subjecting a petroleum' residue substantially free from hydrocarbons having boiling points below 230 C.' and While maintained at a temper- -l tion and While maintaining the mixture at an elevated temperature sufficient' to effect the conversion ofa large portion of such oil treated into low boiling point products;

6. In the process of cracking petroleum oil, the step which consists in subjecting a petroleum residue-substantially free from hydrovc'arbons having boiling points below 230 C.

While maintained at a temperature in excess.

of 200 C. to the action of previously electri- Y cally activated chlorine gas While in the abature in excess o f O C. to the action of previously electrically activated chlorine gas While inthe absence of su'iicient moisture to seriouslyinterfere with the cracking operation.

9. The -method of cracking high boiling point petroleum oil in order to obtaintherevfrom gasolene hydrocarbons, including those ofthe gasolene range, Which comprises subjecting anhydrous 3 letroleum oil having a boiling point in'exces's of 23()o C. to the action offree chlorine gas in the proportion of between 1%and 2%y by Weight-ofthe-petroleum oil treated yand.while maintaining mixture at a temperature not substantially less 'i than the boiling point of the petrolelun oil treated, such chlorine gas being introduced into said oil under a super atmospheric pressure from an external source into the oil treated While in a highly active state due to the activation thereof While in a sufliciently anhydrous condition to permit of effective activation thereof by a high potential electric current and then recovering the low boiling point.

lhydrocarbons resulting from such treatment.

New York and State of Signed at New York city in theicounty of New York this 1st day of May, 1923.

JOHN R. MARDICK. 

